Aminodiphenyl-indolyl-methane dyestuffs and dyeing and printing of polymers and copolymers of acry-lonitrile or asymmetric dicyano-ethylene or of acid-modified aromatic polyesters

ABSTRACT

THIS INVENTION RELATES TO AMINODIPHENYL-INDOLYLMETHANE DYESTUFFS BEING FREE OF SULPHONIC ACID AND CARBOXYLIC ACID GROUPS. THESE DYESTUFFS CAN BE USED IN THE DYEING AND PRINTING OF CERTAIN POLYMERIC PRODUCTS.

United States Patent Office 3,642,823 AMINODIPHENYL-INDOLYL-METHANE DYE- STUFFS AND DYEING AND PRINTING F POLYMERS AND COPOLYMERS 0F ACRY- LONITRILE 0R ASYMMETRIC DICYANO- ETHYLENE OR OF ACID-MODIFIED ARO- MATIC POLYESTERS Roderich Kane and Hans Peter Kiihlthau, Leverkusen,

Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 1, 1967, Ser. No. 657,500 Claims priority, application Germany, Aug. 3, 1966, F 49,865, F 49,866; May 22, 1967, F 52,475 Int. Cl. C07d 27/56 US. Cl. 260-3265 13 Claims ABSTRACT OF THE DISCLOSURE This invention relates to aminodiphenyl-indolylmethane dyestuifs being free of sulphonic acid and carboxylic acid groups. These dyestuffs can be used in the dyeing and printing of certain polymeric products.

The present invention relates to valuable new aminodiphenyl-indolyl-methane dyestuffs of the general formula In this formula R denotes hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester group, an optionally N-substituted carbonamide, acyl, alkylsulphonyl or arylsulphonyl group, R represents hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R means hydrogen, an alkyl, cycloalkyl or aralkyl radical, R denotes hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group or an alkoXy group, R means hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, and X is an anionic radical; the new dyestuffs may contain in the aliphatic, cycloaliphatic and aromatic radicals, including the henzene rings indicated by the above formula, further substituents (non ionic substituents), with the exception of sulphonic acid and carboxylic acid groups. Non ionic substituents include, for example, lower alkyl and alkoxy radicals containing 1-4 carbon atoms; aralkyl, such as benzyl; aralkoxy, such as benzyloxy; aryl, such as phenyl, and penyl radicals which are substituted by nonionic radicals, e.g. chlorophenyl, methylphenyl, ethylphenyl, nitr0- phenyl, cyanophenyl, etc. aryloxy groups, such as phenyloxy; halogen substituents, especially chlorine and bromine; carboxylic acid ester groups, especially caboxylic acid methyl ester and ethyl ester groups; optionally N- substituted carbonamide groups, preferably N-substituents of lower alkyl groups which may be further substituted, eg by Cl, Br and OH; the cyano, nitro, hydroxyl or amino group; alkylsulphonyl, such as methylsulphonyl and ethylsulphonyl; arylsulphonyl, such as benzene-sulphonyl and p-toluene-sulphonyl; acyloxy groups, such as acetoxy and propionyloxy; acylamino groups, such as acetylamino, propionylamino, ethyl-sulphonyl-amino, methyl-sulphonylamino, benzoylamino, benzene, sulpho- 3,642,823 Patented Feb. 15, 1972 wherein R stands for hydrogen, an alkyl, aralkyl or aryl radical, a nitro, cyano, carboxylic acid ester group, an optionally N-substituted carbonamide, acyl or an alkylsulphonyl or aryl-sulphonyl group, R stands for hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R stands for hydrogen, an alkyl, cycloalkyl or aralkyl radical, R stands for hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group or an alkoxy group, R stands for hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, X stands for an anionic radical, K, L and M stand independently for hydrogen or a substituent, p, q and r stand independently for an integer ranging from 1 to 2.

One further group of particularly valuable dyestuffs within the range of the new products of the Formulae I or II corresponds to the formula In this formula R stands for hydrogen or for a lower alkyl radical, especially methyl or ethyl, R' stands for hydrogen, for a lower alkyl radical, especially methyl, ethyl, propyl, butyl, a phenyl radical which may be further substituted by chlorine, bromine, lower alkyl or alkoxy radicals, or for benzyl; R stands for hydrogen or for a lower alkyl radical, such as methyl or ethyl, or for the benzyl radical; R' stands for methyl, phenyl or for phenyl substituted by chlorine, bromine or lower alkyl or alkoxy radicals; and R, stands for hydrogen, for a lower alkyl radical, such as methyl and ethyl, and for benzyl; Z stands for a halogen substituent, especially chlorine or bromine, for a lower alkyl substituent, such as methyl, ethyl or propyl, or for a lower alkoxy substituent, such as methoxy or ethoxy; X represents an anionic radical.

The new dyestufis are obtained when 4-aminobenzophenones of the general formula R2 (IVJ in which R, R and R have the same meaning as above, are condensed with indole derivatives of the general formula in which R and R have the same meaning as above, in the presence of acidic condensing agents to give dyestuffs of the Formulae I, II or III, selecting the starting components free of sulphonic acid and carboxylic acid groups.

The following aminobenzophenones are suitable as starting material for the production of the dyestuffs according to the invention, for example:

4-aminobenzophenone, 4-N,N-dimethylaminobenzophenone, 4-N,N-diethylaminobenzophenone, 4-N,N-dibutylaminobenzophenone, 4-N-methyl-N-hydroxy-ethyl-aminobenzophenone, 4-N-methyl-N-chloroethylaminobenzophenone, 4-N-methyl-N-cyanoethylaminobenzophenone, 4-N-ethyl-N-cyanoethylaminobenzophenone, 4-N-ethyl-N-chloroethylaminobenzophenone, 4-N-ethyl-N-hydroxy-ethylaminobenzophenone, 4-N-butyl-N-hydroxyethylaminobenzophenone, 4-N-butyl-N-chloroethylaminobenzophenone, 4-N,N-dihydroxy-ethylaminobenzophenone, 4-N,N-dichloroethylaminobenzophenone, 4-N-methyl-N-benzylaminobenzophenone, 4-N-ethyl-N-benzylaminobenzophenone, 4-N-phenyl-N-methylaminobenzophenone, 4-N-(4'-ethoxyphenyl)-N-methylaminobenzophenone, 4-N- 2'-ethoxy-phenyl -N-methylaminobenzophenone, 4-N-(4'-chlorophenyl)-N-methylaminobenzophenone, 2-methyl-4-N,N-diethylaminobenzophenone, 2-chloro-4-N,N-diethylaminobenzophenone, 2-methyl-4-N-hydroxy-ethyl-N-ethylaminobenzophenone, 2-chloro-4-N,N-dimethylaminobenzophenone, 2-bromo-4'-N,N-diethylaminobenzophenone, 3-chloro-4-N,N-diethylaminobenzophenone, 4-ethyl-4'-N,N-diethylaminobenzophenone, 4-cyano-4'-N,N-diethylaminobenzophenone, 2-chloro-4'-N-phenyl-N-methylaminobenzophenone, 2-chloro-4-N- (4-ethoxyphenyl) -N-methylaminob enzophenone, 3-chloro-4'-N-phenyl-N-methylaminobenzophenone, 4-phenyl-4-N-phenyl-N-methylaminobenzophenone, 4-ethyl-4'-N-phenyl-N-methylaminobenzophenone, 4-methyl-4'-N-(4-ethoxyphenyl)-N-methylaminobenzophenone, 4-methyl-4'-N,N-dimethyl-aminobenzophenone, 4-methyl-4-N-phenyl-N-methylaminobenzophenone, 4-cyano-4'-N,N-dimethylami'nobenzophenone, 4-carbomethoxy-4'-N,N-dimethylaminobenzophenone, 4-methylsulphonyl-4'-N-phenyl-N-methylaminobenzophenone.

Suitable indole derivatives are, for example:

2-methylindole, 2-phenylindole, 2,5-dimethylindole, Z-methyl-S-chloroindole, 2-phenyl-5-methylindole, 2-phenyl-5-chloroindole, 1,2-dimethylindole, 1-methyl-2-phenylindole, 1,2,5-trimethylindole, 1,5-dimethyl-Z-phenylindole, 1,2-dimethyl-5-chloroindole, 1-methyl-2-phenyl-5-chloroindole, 1-ethy1-2-methylindole,

4 l-ethyl-2-phenylindole, 1-ethyl-2,5-dimethylindole, 1-ethyl-2-phenyl-S-methylindole, 1-ethyl-2-methyl-5-chloroindole, 1-ethyl-2-phenyl-5-chloroindole, l-benzyl-Z-methylindole, 1,4,7-trimethyl-Z-phenyl-indole, 1-n-butyl-2-phenylindo1e, 1-isobutyl-2- (4'-chlorophenyl)-4,6-dimethylindole, l-cyanoethyI-Z-Inethylindole, l-cyanoethyl-Z-phenylindole.

Suitable acidic condensing agents are, for example:

Hydrochloric acid, sulphuric acid, phosphoric acid, phosphorus oxychloride, thionylchloride, phosgene, zinc chloride, aluminium chloride, tin chloride or p-toluenesulphonic acid.

The reaction may be carried out in the presence or absence of an inert solvent. Suitable solvents are, for example, chlorobenzene, o-dichlorobenzene, toluene, xylene, benzene, ligroin, dioxan, cyclohexane, carbon tetrachloride, chloroform and, in some cases, also methanol, ethanol and acetone.

The reaction is generally carried out at an elevated temperature, eg at 40-160 C., preferably at -l20.

The anionic radicals X can be inorganic as well as organic ions; there may be mentioned by way of example: Cl-, Br", 1-, CH SO C H SO p-toluene-sulphonate, H50 benzenesulphonate, p-chlorobenzene-sulphonate, phosphate-, acetate-, formate-, propionate-, succinate-, oxalate-, lactate-, maleinate-, crotonate-, tartrate-, [BF citrate-, N0 1 perchlorate-, ZnCl The type of anionic radicals is of no importance for the properties of the dyestufis provided substantially colourless radicals are used which do not impair the solubility of the dyestuffs in an undesirable manner.

According to another process, part of the dyestuffs according to the invention can also be obtained by condensing benzoyl indoles of the general formula in which R, R and R have the same meaning as above, while R stands for hydrogen, for an alkyl, cycloalkyl or aralkyl radical, and R stands for an alkyl, cycloalkyl, aralkyl or aryl radical,

in the presence of acidic condensing agents.

Examples of benzoyl indoles of the general Formula VI which are suitable for the production of the dyestuffs according to the invention include:

1-methyl-2-phenyl-3-benzoylindole, 1,2-dimethyl-3-benzoylindole,

1,2,5 -trimethyl-3-benzoylindole, 1,5-dimethyl-2-phenyl-3 -b enzoylindole, 1,Z-dimethyl-3-benzoyl-5-chloroindole, 1-methyl-2-phenyl-3-benzoyl-5-chloroindole, l-ethyl-2-methyl-3-benzoylindole, 1-ethy1-2-phenyl-3-benzoylindole, 1-benzyl-2-methyl-3-benz0ylindole, 1,4,7-trimethyl-2-phenyl-3-benzoyl ndole, 1-n-butyl-2-phenyl-3-benz0ylindole, l-cyanoethyl-2-methyl-3-benzoylindole, 1-cyanoethyl-2-phenyl-3-benzoylindole, l-methyl-Z-(2-chloropheny1)-3-benzoylindole,

1-methyl-2-phenyl-3- 2'-chlorobenzoyl) -indole, 1-methyl-2-phenyl-3-( 3-chlorobenzoyl -indo1e, 1-methy1-2-phenyl-3- (4'-methylbenzoyl -indo1e, 1,2-dimethyl-3- (2'-chlorobenzoyl) -indole,

1 ,2-dimethyl-3- 3 '-chlorobenzoyl -indole, 1,2-dimethyl-3 (4-methylbenzoyl) -indole and 1-ethyl-2-phenyl-3- (2'-chlorobenzoyl) -indole.

Suitable aromatic amines of the general Formula VII are, for example:

Acidic condensing agents suitable for the present process are, in particular, phosphorus oxychloride, thionyl chloride, phosgene, zinc chloride, aluminium chloride, etc.

Another suitable process for the preparation of the new dyestuffs consists in condensing benzanilides of the general formula R (VIII) in which R has the same meaning as above, while R stands for hydrogen or the alkyl radical, and R stands for an aromatic radical,

with aromatic amines of the general Formula VII in the presence of acidic condensing agents and subsequently with indoles of the general Formula V without isolating the intermediate products.

The following benzanilides (VIII) which are suitable for the present process may be mentioned by way of example: benzanilide, 2-chlorobenzanilide, 3-chlorobenzanilide, Z-methylbenzanilide, 3-methylbenzanilide, 4- methylbenzanilide, 2-methoxybenzanilide, 2-ethoxybenzanilide, 2,4-dimethylbenzanilide, 2,5-dichlorobenzanilide and 2,6-dichlorobenzanilide.

The same compounds indicated for the second method of procedure are also suitable as aromatic amines (VII) for this method of production. Those indole compounds which have been mentioned as suitable for the first method of production may also be used. Phosphorus oxychloride, thionylchloride, phosgene, zinc chloride, aluminium chloride, etc. are suitable as acidic condensing agents also in this case.

The products obtainable according to the present process are extraordinarily valuable dyestuffs which can be used for the dyeing and printing of materials of leather, tannin-treated cotton, cellulose acetate, synthetic superpolyamides and superurethanes, as well as for the dyeing of lignin-containing fibres, such as coconut fibres, jute and sisal. They are also suitable for the production of liquid writing inks, stamping inks, ball point pastes, and they may also be used in offset printing. Above all, they are eminently suitable for the dyeing and printing of materials which are composed partially or completely of polymerised acrylonitrile and/or vinylidene cyanide, or which are composed partially or completely of acid-modified aromatic polyesters, such as sulphonic acid groupcontaining polyethylene terephthalate, and are here distinguished by very good fastness to light, wet processing, rubbing and sublimation. Furthermore, they possess a very good afiinity for these fibres and have a good fastness to cross-dyeing. With anionic precipitants, such as aluminum oxide, tannin, phosphotungstic (molybdic) acids, the dyestuffs form pigments which are fast to light and can advantageously be used for printing paper.

The present invention further relates to the dyeing and printing of polymers and copolymers of acrylonitrile or asymmetric dicyanoethylene, or of acid-modified aromatic polyesters. In accordance with the invention it has been found that shaped articles, such as fibres, foils, fabrics and the like, obtained from polymers or copolymers of acrylonitrile or asymmetric dicyanoethylene, or from acid-modified aromatic polyesters can be dyed and printed in very fast shades by using as dyestuffs compounds which are free from sulphonic acid and carboxylic acid groups and correspond to the general formula in the above formula R represents hydrogen, an alkyl or aryl group, a carboxylic acid ester group, an optionally N-substituted carbonamide group, or an alkoxy group; R means hydrogen or an alkyl, aralkyl, cycloalkyl or aryl radical; R means hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical; R means hydrogen, an alkyl, cycloalkyl or an aralkyl radical; R means hydrogen, halogen, such as Cl and Br, alkoxy, aralkoxy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, cyano, trifiuoromethyl and carboxylic acid ester groups, optionally N-substituted carbonamide groups, acyl groups and alkylsulphonyl or arylsulphonyl groups, and X is an anion; the aromatic and (cyclo) aliphatic radicals, including the benzene rings according to the above formula, may carry further substituents (non-ionic substituents), with the exception of sulphonic acid and carboxylic acid groups.

Suitable aryl radicals R, R R and R are preferably those of the benzene series, such as phenyl, 4-methylphenyl-4-chlorophenyl, 4-methoxyphenyl, 2 methoxyphen yl or 2-chlorophenyl. Suitable carboxylic acid ester groups are, for example, the carboxylic acid methyl or ethyl ester; suitable carbonamide groups are, for example, the carboxylic acid methylamide and dimethylamide group.

Suitable alkyl radicals R, R R R and R are, in particular, lower alkyl radicals containing 1-5 carbon atoms, such as methyl, ethyl and butyl radicals which may also contain non-ionic substituents. Suitable non-ionic substituents are, for example, lower alkyl and alkoxy radicals containing 1-4 carbon atoms; aralkyl, such as benzyl; aralkoxy, such as benzyloxy; aryl, such as phenyl, and phenyl radicals substituted by non-ionic radicals, e.g. chlorophenyl, methylphenyl, ethylphenyl, nitrophenyl, cyanophenyl etc.; aryloxy groups, such as phenyloxy; halogen substituents, especially Cl and Br; carboxylic acid ester groups, especially carboxylic acid methyl ester and ethyl ester groups, optionally N-substituted carbonamide groups, lower alkyl groups being preferred as N-substituents which may be further substituted, eg by Cl, Br and 0H; the cyano, nitro, hydroxyl or amino group; alkylformula wherein R stands for hydrogen, alkyl, aryl, carboxylic acid ester group, carbonamide or substituted carbonamide group or alkoxy, R stands for hydrogen or an alkyl, aralkyl, cycloalkyl or aryl radical, R stands for hydrogen, an alkyl, aralkyl, cycloalkyl or aryl radical, R stands for hydrogen, an alkyl, cycloalkyl or aralkyl radical, R stands for hydrogen, halogen, an alkoxy, aralkoxy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, cyano, trifiuoromethyl radical or a carboxylic acid ester radical, carbonamide or substituted carbonamide, acyl, alkyl sulphonyl or arylsulphonyl groups, X stands for an anion, K, L and M stand independently for hydrogen or a substituent, p, q and r stand independently for an integer ranging from 1 to 2.

The invention also concerns polyacrylonitrile containing at least 50 percent of acrylonitrile, or acid-modified aromatic polyesters dyed with a sulphonic acid groupfree and carboxylic acid group-free compound of the Formulae II, III, X or XI.

A further group of preferred dyestuffs to be applied corresponds to the formula N 1'14 (X1) in which R stands for a lower alkyl radical, preferably methyl or ethyl, or for a phenyl radical which may be substituted by chlorine, bromine, lower alkyl or lower alkoxy radicals; R stands for hydrogen, a lower alkyl radical, such as CH --C H n-C H nC H or benzyl, R stands for hydrogen or for a lower alkyl radical, such as methyl or ethyl, or for the benzyl radical, or for a phenyl radical which may be substituted by chlorine, bromine, lower alkyl or lower alkoxy; R stands for hydrogen, a lower alkyl radical, such as methyl or ethyl, or benzyl; n is the number 0, l, 2 or 3; Z stands for a halogen substituent, especially C1 or Br, for a lower alkyl substituent, such as methyl, ethyl or propyl, or for a lower alkoxy substituent, such as methoxy or ethoxy; X represents an anionic radical.

The dyestuffs of the above general Formulae IX, X and XI are obtained, for example, by condensing in the 3- position 4-aminobenzo-phenones of the general formula ll RQ (XII) in the presence of acidic condensing agents with indole derivatives of the general formula The dyestulfs can also be prepared by reacting compounds of the general formula H. i R4 (XIV) with aromatic amines of the general formula n the presence of acidic condensing agents.

Another process for the production of the dyestuffs to be used according to the invention consists in condensing compounds of the general formula in which R stands for a halogen atom, the oxy group, for an alkoxy, acyloxy or amino group, with indole derivatives of the Formula XIII in the presence of acidic condensing agents, and by reacting the resultant intermediate products of the general formula R4 (XVII) with primary aromatic amines with the exchange of the radical R for an amino group. In the preceding Formulae XII to XVII, the radicals R, R R R R and X have the same meaning as given above.

The anionic radicals X- can be inorganic as well as organic ions; the following may be mentioned by way of example: Cl", Br, I, CH SO C H SO p-toluene sulphonate-, HSO4 benzene sulphonate-, p-chlorobenzene sulphonate-, phosphate-, acetate-, formate-, propionate-, butyrate-, oxalate-, lactate-, maleinate, succinate-, crotonate-, tartrate-, [BF citrate-, NO perchlorate-, ZnCl etc. The type of the anionic radicals is immaterial for the use of the dyestuffs, provided they are largely colourless radicals which do not impair the solubility of the dyestuffs in an undesirable way.

For the dyeing with the basic dyestuffs of the above general formula, there are especially suitable: flocks, fibres, filaments, ribbons, woven and knitted fabrics of polyacrylonitrile or of copolymers of polyacrylonitrile with other vinyl compounds, such a vinyl chloride, vinyl- Examples of suitable dyestuffs of the general Formula IX are set out in the following table:

A B D P); enyl 4N-phenyl-N-rnethylarninophenyll-methyl-2-pheny1-5chloroindoly1-3- Phenyl- 4-N-phenyl-N-methy1aminophenyl- 1-ethyl-2-methy1indo1y1-3- Phenyl 4-N-phenyl-N-methylaminophenyl- 1-ethyl-2-pheny1indolyl-3- Phenyl- 4-N-pheny1-N -methylam1nophenyl- 1-ethyl-2,fi-dimethyllndolyl-ii- Phenyl- -N-phenylN-methylaminophenyl- 1ethyl-2-phenyl-5-methy1indo1yl-3- P1 enyl- 4-N-pheny1-N-methylaminoph enyl- 1-ethyl-2-methy1-5-eh1oroindolyl-3- Ph enyl- 4-N-phenyl-N-methylaminophenyll-ethyl-2-phenyl-fi-chloroindolyl-a- Phenyl- 4-N-pheny1-methylamlnophenyl- 1-benzyl-2-methylindolyl-S- Phenyl- 4-N-phenyl-N-methylaminophenyl- 1,4,7-tr1methyl-2-phenylindolyl-3- Phenyl- 4-N-pheny1 N-methylamlnophenyl- 1-n-buty1-2-phenylindoly1'3- Phenyl- 4-N-phenyl'N-methylaminophenyl- 1-ls0butyl-2-(4-chloropheny1) -4,6-dimethylindolyl-3- Phenyl- 4-N-phenyl-N-methylaminophenyll-cyanoethyl-2-methylindolyl-3- Phenyl- 4-N-phenyl-N-methylaminophenyll-cyanoeth y1-2-pheny1indolyl3- Phenyl- 4-N-phenyl-N-methylamlnophenyl- 1-methy1-2-phenyl-5-methoxyindolyl-El- Phenyl- 4-N-phenyl-N-methylarninophenyl- 1-methyl-2-phenyl-5e thoxyindolyl-3- Phenyl- 4-N-phenyl-N-methylamlno-phenyll-methyl-2-phenylindolyl-3- Phenyl- 4-N-(4ethoxyphenyl) -N-methylaminophenyl- 1-methyl-2-phenylindoly1-3- Phenyl- 4-N -pheny1-N -methyla.minophenyl- 1,2-dlmetl1yllndolyl-3- Phenyl- 4- -(4-ethoxyphen yl) -N-methylaminophenyl- 1,2{dimethylindolyl-3- Phenyl- 4-N,N-dimethylammophenyll-methyl-Z-phenylindolyl-El- Phenyl- 4-N,N-dlethylaminophenyll-methyl-2-phenylindo1yl-3- 2-chlorophenyl- 4-N-phenyl-N-methylaminophenyll-m ethy12-phenylindolyl-3- 2-eh1or0phenyl- 4-N phenyl-N -methy1aminophenyl- 1,2-dimethyl1ndolyl-3- 2-chloropheny1- 4-N-(4-ethoxyphenyl)-N-methylamlnophenyll-methyl-Z-phenylindolyl-3- 2-chlorophenyl- 4-N-(4-eth0xyphenyl) -N-methylaminophenyl- 1,2-d1methylindolyl3- 2-chlorophenyl- 4-N,N-dimethylam1nophenyll-methyl-2-phenyllndolyl-3- 2-chlorophenyl- 4-N,N-diethylaminopbenyl- 1-methyl-2-phenylindolyl-3- 2-chlorophenyl- 4,N ,N-dlmethylaminophenyl- 1,2-dimethylindulyl-3- 2-ch1orophenyl- 4-N,N-diethylaminophenyl- 1,2-dimethy1indo1y1-3- B-chlorophenyl- 4-N,Ndiethy1ami.nophenyl- 1-methyl-2-phenylindolyl-3- 3-ehlorophenyl- 4-N,N-diethylaminophenyl- 1,2-dimethyllndolyl-3- 4-ehlorophenyl- 4-N,N-di methy1aminophenyll-methyl-Z-phenylindolyl-ii- 4-methylphenyl- 4-N,N-d1ethylaminopheny1- l-methyl-Z-phenylindolyl-fii- 4-methoxypheny1 4-N-phenyl-N-methylaminophenyll-methyl-2-phenylindolyl-3- Phenyl- 4-aminopheny1- 1-methyl-2-phenylindolyl-3- Phenyl- 4-aminophenyl- 1,2-dimethylindolyl-3- Ph enyl- 4-aminophenyl- 2-methylindolyl-3- Phenyl- 4-N-phenyl-N-methylamlnophenyl- 2-phenylindoly1-3- Phenyl- 4-phenylaminopheny1- l-methyl-Z-phenyllndolyl-3- Phenyl- 4-N-(4-methylphenyl)aminophenyb 1-methyl-2-phenylindo1yl-3- Phenyl- 4-N- (3 -methylphenyl) -amlnophenyll-methyl-2-phenylindolyl-3- Ph enyl- 4-N-(2-methylphenyl) -a.mlnophenyl- 1-methyl-2-phenylindolyl-ll- Phenyl- 4-N-(4 -chloropheny1) -aminophenyl- 1-methyl2-phenylindolyl-Z% Phenyl- 4.N (4ace tylaminopheny1) -aminophenyl- 1-methyl-2-phenylindolyl-3- Phenyl- 4-N-(4'-methylsulfonyl-phenyl) -aminopheny1- l-methyl-Z-pheny1indo1y1-3- Phenyl- 4-N-(2,6-d1methylphenyl) -a.minophenyll-methyl-2-phenylindolyl-3- Phenyl- 4N-phenyl-N-methylaminoph enyl- 2,5-dimethylindolyl-3- Phenyl- 4-N-phenyl-N-methylaminophenyl- 2-m'ethyl-5-ch1oroindolyl-3- Ph enyl- 4-N-phenyl-N-methylarninophenyl- Z-phenyl-fi-methylindolyl-B- Phenyl- 4-N-phenyl-N-methylaminophenyl- 1,2,6-trimethylindolyl-8- Phenyl- A-N-phenyl-N-mathylaminophenyl- 1,5 dlmethyl-2-phenyl1ndolyl-3- Phenyl- 4-N-phenyl-N-methylaminophenyl- 1,2-dimethyl-5-ch1oroindoly1-3- idene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, vinyl alcohol, acrylic and methacrylic acid esters and amides, and asymmetric dicyanoethylene, particularly those polymers or copolymers con taining at least 50 percent acrylonitrile. The dyestulfs can likewise be applied for the dyeing and printing of acidmodified aromatic polyesters in form of their flocks, fibres, foils,'.filaments, ribbons, woven and knitted fabrics. Examples of acid-modified aromatic polyesters are e.g. polycondensation products of sulphoterephthalic acid and ethylene glycol (type Dacron X 64 of E; I. du Pont de Nemours and Company), such as described in Belgian patent specification 549,179 and US. Patent specification 2,893,816.

Dyeing can be effected from a weakly acidic bath; it is expedient to introduce the material into the dyebath at 40-60" C. and to dye at boiling temperature. It is alsopossible to dye under pressure at temperatures above 100 C. Furthermore, the dyestuffs may be added to spinning solutions for the production of,polyacrylonitrilecontaining fibres or to apply them on the not-orientated fibre;

The dyeings obtainable according to the invention are characterised by bright, predominantly red, violet, blue and green shades of very good fastness to light and washing. The good affinity of the dyestuffs and their good fastness to cross-dyeing in an acetic acid or sulphuric acid medium should also 'be emphasized.

Dyestufls which are not substituted in the phenyl radical A in the p-position, or contain as non-ionic substitutuent R halogen, a lower alkyl or alkoxy group and/or in the o-position of the radical A a halogen atom, such as C1 or Br, a lower alkyl or alkoxy group, have a preferred interest from the technical point of view; in particular, the derivatives which are substituted in the 0- position to the central carbon atom are distinguished by especially clear shades.

EXAMPLE 1 37.8 parts by weight N-phenyl-N-methylaminobenzophenone, 27.2 parts by weight l-methyl-Z-phenyl-indole and 35 parts by weight phosphorus oxychloride are heated together to C. and the mixture is kept at this temperature for 3 hours. The hot melt is added to 600 parts by volume of water at 50 C., and the pH value is adjusted to 2 by the addition of parts by volume of a 20% sodium acetate solution. Precipitation of the dye-" stufi is then completed by the addition of 30 parts by weight of sodium chloride and the mixture is stirred fon some hours. The resultant dye resin is separated, dissolved in 4000 parts by volume of boiling water, the solution is clarified with active charcoal and, when the solution is somewhat cooler, the dyestuff is precipitated by the addition of 90 parts by volume of a solution of zinc chloride in an equal amount by weight of water. The dyestutf is stirred for some time, filtered off with suction and washed 11 with a 10% sodium chloride solution. The dyestufi? thus obtained corresponds to the formula @lD O and dyes fibres of polyacrylonitrile in a bluish green shade which is fast to light.

Valuable dyestuffs are also obtained when in the preceding example there are used, instead of l-methyl-Z- phenylindole, the equivalent amounts of the indole derivatives set out in the following table.

Shade on polyacry- Indole derivative: lonitrile fibres 1-cyanoethyl-2-methylindole Bluish green. 1-ethyl-2-phenyl-7-chloroindole Do. 1,6-dimethyl-Z-phenylindole Do. l-isobutyl-Z-phenylindole Do. l-ethy1-2-pheny1-6-methylindole Do. 1-n-butyl-2-pheuyl-6-methylindole Do. Ln-butyl-Z-phenylindole Do.

EXAMPLE 2 parts of weight 4-N,N-dimethylaminobenzophenone, 41.4 parts by weight 1-methyl-2-phenylindole and parts by weight phosphorus oxychloride are mixed and the mixture is heated at C. for 3 hours. The hot melt is poured into 1000 parts by volume of water at 50 C. and the reaction mixture is adjusted to a pH value of 2 with 320 parts by volume of a 20% sodium acetate solution. After the solution has cooled, the dyestuff is precipitated by the addition of 100 parts by weight of sodium chloride and parts by volume of a solution of zinc chloride in an equal amount by weight of water. For further purification, the dyestutf is dissolved in boiling water, clarified with active charcoal and precipitated by the addition of 30 parts by volume of a zinc chloride solution. The dyestufi thus obtained dyes fibers of polyacrylonitrile in a greenish blue shade which is fast to light.

1-ethyl-2-phenylindole Bluish green. When the reaction is carried out according to the proc- 1-ethyl-2-methylindole Blue. esses described above with the aminobenaophenones and 1-ethyl-Z-phenyl-S-methyl-indole Green-blue. 30 indole derivatives set out in the following table, dyestuifs 1,5-dimethyl-Z-phenylindole Bluish green. are also obtained which are distinguished by very good 1-cyanoethyl-2-phenylindole Do. tinctorial properties.

Amiuobenzopheno ne Indole Shade on polyacrylonitril -dimethylaminobenzophenone LZ-dimethylindole Bluish violet.

o 2-methyl-1-etl1yl-6,7-benzoindole Blue-grey.

4-diethylaminobenzophenone l-methyl-2 phenylindole Blue.

Do Zmethylindole Violet.

Do Z-phenylindole Green-blue.

D o 2-methyl-l-ethyl-6,7-benzoindole. G rey-violet. 4-dimetl1ylamin0-4-metliylbenzophenone. 1,2-dirnethylind0le Reddish violet.

Do 1methyl-2-phenylindole. Greenish blue. 4-dimethylamino-3-cl1lorobenzophenone 1,2-dimethylind e Reddish blue.

0 1-rnethy1-2-pheny1indole- Blue. 4-dimethylamino-2-chlorobenzophenone hylindole Reddish blue.

Do 1-methyl-2-phenylindole. Blue. 4-diethylaminobeuzophenone 1,2-dimethylindole Blue-violet. 4-diethylamino-4-methylbcnzophenone. do Bluish violet.

1-methyl-2-phenylindole. Blue-green.

o 4-dimethylamino-2-ehloro-benzophenone.

o 4-diethylamino-4-methylbenzophenone- 4-dimethylamino-2,5-diehl0ro-benz ophenone D0 4-di1Bethylamluo-3-methyl-4-nitrobenzophenone o 4-diethylamino-2-ehloro-benzophenone.

O 4-cyanoethyl-methylaminobenzopheuoneo 4-die5hylamino-3-methylbenzophenone 4-(p-ethoxyphenyl)-methylan1ino-3-ehlorobenzophenone.. 4-(p-ethoxyplienyl)-methylamino-3-chloro-benzophenone orobenzephenone.

o i-plilgnylmethylatni11o-4-methyl-benzoplienone Blue.

Strongly greenish blue. Reddish violet. Reddlsh blue. Greenish blue. Turquoise.

Greenish blue.

1,2-dimethylindole l-methyl-2-phenylindole... 1,2-dimethylindole 1-methyl-2-phenyllndolo 1,2-dimethylind0le l-methyl-Z-phenylindole. 1,24iimethylindole l-methyl-2-phenylindole. Bluish green. Z-methylindole Blue. 1-methyl-2-phenyhudole. Green.

LZ-dimethylindole Z-methylindole 2-phenylindole 2-methylindole Bluegrey. Bluish bordeaux. Blue-green. Reddish blue.

2-phenylindole- Greenish blue. Z-meth ylindole Bluish violet. 2-phenylindole Greenish blue. 2-methylind0le. Violet. 1,2-dimethylindole. Blue. l-methyl-Q-phenylindole. Greenish blue. 2-rnethylindole Reddish blue.

2-phenylindole Greenish blue.

Greenish blue. Bluish green. Reddish blue. Greenish blue. Blue-green. Reddish violet. Greenish blue. Bluish green.

LZ-dimethylindole. 1-ruethyl-2-pl1enyla 2-methylindole Z-phgnyllndole o -methylindole 1,2-dimethylindo 1-methyl-2-phenylindol D0. Greenish blue.

o o. 1-methyl-2-phenylindole Bluish green.

17 EXAMPLE 4 Polyacrylonitrile fibres are introduced at 40 C. into an aqueous bath having a goods-to-liquor ratio 1:40 and containing, per litre, 0.75 g. 30% acetic acid, 0.38 g. sodium acetate and 0.3 g. of the amino-diphenylindoylmethane dyestulf illustrated by the formula in Example 1. The bath is heated to boiling temperature within 20- 30 minutes and kept at this temperature for 30-60 minutes. The polyacrylonitrile fibres are subsequently rinsed and dried. A bluish green dyeing of very good fastness to light is obtainedwhich is also distinguished by a very good fastness to cross-dyeing in an acetic acid and sulphuric acid bath.

- EXAMPLE 5 A stamping ink which yields clear, strong prints is prepared from 2 parts by weight of the amino-diphenylindolyl-methane' dyestuff, the production of which has been described in Example 2, 60 parts by Weight glycerol, 20 parts by weight of water and 20 parts by weight of spirit.

EXAMPLE 6 East-Indian bastard skin which has been prepared for dyeing in usual manner is dyed in a milling drum at 40 for 45 minutes in a goods-to-liquor ratio 1:10 with 1% of the dyestulf described in Example 1 which waspreviously pasted with an equal amount of 30% acetic acid. The leather is finished in known manner. A greenish blue dyeing of good fastness properties is obtained.

EXAMPLE 7 197 parts by weight benzanilide and 22.7 parts by weight N-methyl-4-ethoxy-diphenylamine are heat at 100 C. for 3 hours with 40 parts by weight phosphorus oxychloride. 20.7 parts by weight l-methyl-2-phenyl-indole are subsequently introduced and the mixture is heated at 100 C. for a further 3 hours. The hot melt is poured into 1000 parts by volume of water andadjusted to pH 2 with 275 parts by volume of a 20% sodium acetate solution. The reaction mixture is further stirred for several hours, the dye resin is separated and dissolved in 3000 parts by volume of boiling water with the addition of 300 parts by volume of glacial acetic acid and the solution is clarified with active charcoal. The dyestuff is precipitated from the filtrate by the addition of 50 parts by volume of a solution of zinc chloride in an equal amount of water.

The dyestuif dyes materials of polyacrylonitrile in a bluish green shade of very good fastness properties.

. EXAMPLE 8 Acid-modified polyglycol terephthalate fibres of the type Dacron 64 (E. I. du Pont de Nemours and Company) and asffor instance, described in the Belgian patent specification 549,179 and the US. patent specification 2,893,816 are introduced at 20 C. into a dye-bath containing per litre 3 g. of sodium sulphate, 0.5 to 2 g. of an oleylpolyglycol ether, prepared with 50 mol of ethyleneoxide, 2.5 to 5 g. of diphenyl and 0.3 g. of the dyestuif of Example 1 and which has been adjusted to a pH of 4.5 to 5.5 with acetic acid. The liquor-to-goods ratio is 40:1. The temperature of the dye-bath is heated within 30 minutes to 98 C. and the bath kept at this temperature for 60 minutes. The dyed fibres are subsequently rinsed with water and dried. A bluish green dyeing of very good fastness properties is obtained.

EXAMPLE 9 Acid-modified polyglycol terephthalate fibres as described in Example 8 are introduced at 20 C. into a dyebath containing per litre 6 to 10 g. of sodium sulphate,

0.5 to 1 g. of an oleylpolyglycol ether prepared with 50 mol of ethyleneoxide, 0 to 15 g. of dimethylbenzyl-dodecyl-ammoniumchloride and 0.3 g. of the dyestuif of Example 1 and which has been adjusted to a pH of 4 to 5 with acetic acid. The liquor-to-goods ratio is :1. The temperature of the dye-bath is heated within 30 minutes to 120 C. and the bath kept at this temperature for 60 minutes. The dyed fibres are subsequently rinsed with water and dried. One obtains a bluish green dyeing of very good fastness properties.

The dyestuffs mentioned in the preceding examples may likewise be used for the dyeing of acid-modified aromatic polyester fibres according to the methods described in Examples 8 and 9 thus yielding valuable shades which are similar or equal to the shades obtained on polyacrylics.

EXAMPLE 10 Fibres of polyacrylonitrile are introduced at 40 C. into an aqueous bath having a goods-to-liquor ratio 1:40 and containing, per litre, 0.75 g. of a 30% acetic acid,

0.38 g. sodium acetate and 0.3 g. of the aminodiphenylindolyl-methane dyestutf of the formula the. preparation of which is described below. The bath is heated to boiling temperaturewithin 20-30 minutes and kept at thistemperature for 30-60 minutes. The polyacrylonitrile fibres are subsequently rinsed and dried. A bluish green dyeing of very good light fastness is obtained which is also distinguished by a very good fastness to cross-dyeing in an acetic acid and sulphuric acid bath. The dyestuff was obtained in the following manner: 216 parts by weight 4-chlorobenzophenone and 207 parts by weight l-methyl-Z-phenylindole are dissolved at 70 C. in 1800 parts by volume of chlorobenzene, followed by the addition of 160 parts by weight of anhydrous zinc chloride. 306 parts phosphorus oxychloride are subsequently introduced into the reaction mixture which is stirred at 120-l25 C. for 18 hours. The compound, which precipitates in crystalline form upon cooling, is stirred for some time, filtered off with suction, Washed with cold chlorobenzene and dried. 20 parts by weight of this compound are introduced into 60 parts by weight 4- phenetidine heated to C. and the melt, which instantly adopts a blue-green colour, is stirred at C. for 3 hours. The hot melt is poured on to 500 parts by volume of ice-water and 50 parts by volumehydrochloric acid (d=1.19), whereupon the dyestuif precipitates in crystalline form. After stirring for several hours, it is filtered off with suction and purified by recrystallisation from 10% acetic acid with the addition of sodium chloride.

With the same good result, those dyestuffs can also be used for the dyeing of polyacrylonitrile which are obtained by the reaction of the aromatic amines set out in the table below with the condensation product of 4- chlorobenzophenone and 1-methyl-2-phenyl-indole.

Shade of dyeing Aniline derivative: on polyacryonitrile Aniline Bluish green. 4-hydroxyethoxyaniline Do. 4-toluidine Do.

3-toluidine Do. 2-toluidine Greenish blue. 4-chloroaniline Bluish green. 2-chloroaniline Blue-green. 3-chloroaniline Greenish blue. 1-amino-4-methy1-3- chlorobenzene Bluish green. 3,4-dichloroaniline Strongly bluish green. 4-methylsulphonylaniline Bluish green. N-acetylphenylenediamine-1,4 Turquoise. 4-anisidine Bluish green. 3-anisidine Do. Z-amino-1,3-diethylbenzene Greenish blue. 5-amino-1,3-di(trifiuoromethyl)-benzene Grey-blue. 4-amino-3-methyl-l-cyclohexylbenzene Green-blue. 5-amino-1,3-dimethylbenzene Bluish green. 2,6-diisopropylaniline Greenish blue. 2-amino-1-ethylbenzene Green-blue. 4-a mino-1,3-dimethylbenzene Do. 2-isopropylaniline Do. Z-amino-1,4-dimethylbenzene Do.

EXAMPLE 11 the preparation of which is described below 50 parts by weight thiodiethylene glycol, 30 parts by weight cyclohexanol and 30 parts by weight 30% acetic acid, and the resultant solution is added to 500 parts by weight of crystal gum (gum arabic as thickening agent). Finally, 30 parts by weight of a zinc nitrate solution are also added. The resultant print is dried, steamed for 30 minutes and subsequently rinsed. A bluish green print with very good fastness properties is obtained.

The dyestuif is obtained as follows:

37.8 parts by weight N-phenyl-N-methylaminobenzophenone, 27.2 parts by weight 1-methy1-2-phenyl-indole and 35 parts by weight phosphorus oxychloride are heated together to 100 C. and the mixture is kept at this temperature for 3 hours. The hot melt is added to 600 parts by volume of warm water at 50 C. and the pH value is adjusted to 2 by the addition of 140 parts by volume of a 20% sodium acetate solution. The precipitation of the dyestutf is completed by the addition of 30 parts by weight of sodium chloride and the reaction mixture is stirred for some hours. The dye resin is separated, dissolved in 4000 parts by volume of boiling water, the solution is clarified with active charcoal and the dyestuff precipitated, when the solution is somewhat cooler, by the addition of 90 parts by volume of a solution of zinc chloride in an equal amount by weight of water. The dyestuff is stirred for some time, filtered olf with suction and washed with a 10% sodium chloride solution.

With the same good result, the dyestuffs can be used which were obtained by the reaction of the indole derivatives set out in the table below, instead of l-methyl-Z- phenylindole:

Hade' on polyacryloni- Indole derivative: trile fibres.

2-phenylindole Bluish green. Z-methylindole Greenish blue. 1,2-dimethylindole Do. l-methyl-Z-phenyl-S- methoxyindole Blue-green. 1-ethyl-2-phenyl-indo1e Bluish green. l-ethyl-2-methyl-indole Blue. 1-ethy1-2-phenyl-S-methylindole Green-blue. 1,5-dimethyl-2-phenylindole Bluish green. l-cyanoethyl-Z-phenylindole Do. l-cyanoethyl-Zmethylindole Do. 1-ethyl-2-phenyl-7-chloroindole Do. l,6-dimethyl-2-phenyl indole Do. 1-isobutyl-2-phenylindole Do. 1-ethy1-2-phenyl-6- methylindole Do. 1-n-butyl-2-phenyl-6- methylindole Do. 1-n-butyl-2-phenyl-indole Do.

EXAMPLE 12 Fibres of polyacrylonitrile are introduced at 40 into an aqueous bath having a goods-to-liquor ratio 1:40 and containing, per litre, 0.75 g. 30% acetic acid, 0.38 g. sodium acetate and 0.3 g. of the aminodiphenylindolylmethane dyestutf of the formula ZnCh the preparation of which is described below. The bath is heated to boiling temperature Within 20-30 minutes and kept at this temperature for 30-60 minutes. The polyacrylonitrile fibres are subsequently rinsed and dried. They show a greenish blue dyeing of very good fastness to light.

The dyestuff was obtained in the following manner:

45 parts by weight 4-dimethyl aminobenzophenone, 41.4 parts by weight 1-methyl-2-phenylindo1e and 50 parts by weight phosphorus oxychloride are mixed and the mixture is heated at C. for 3 hours. The hot melt is poured onto 1000 parts by volume of water at 50 C. and the reaction mixture adjusted to a pH of 2 with 320 parts by volume of a 20% sodium acetate solution. When the solution has cooled, the dyestuff is precipitated by the addition of 100 parts by weight sodium chloride and parts by volume of a solution of zinc chloride in an equal amount by weight of water. For further purification the dyestulf is dissolved in boiling water, clarified with active charcoal and precipitated by the addition of 30 parts by volume of a zinc chloride solution.

suction and the dyestulf is purified by recrystallisation from water and precipitation with sodium chloride.

With the same good result, those dyestuffs can be used for the dyeing of polyacrylonitrile which are obtained by the reaction of the indoles set out in the following table with 4-amino-benzophenone:

Shade of the dyeing on Indole: polyacrylonitrile Z-methylindole Red-violet. l-methyl-Z-phenylindole Blue-violet. 1-ethyl-2-methylindole Bluish ruby. 1-ethyl-2-phenylindole Bluish violet. 1,5-dimethyl-2-phenylindole Do. 1-ethyl-2-pheny1-5-methylind Do.

EXAMPLE 17 Acid-modified polyglycol terephthalate fibres as described in Example 16 are introduced at 20 C. into a dyebath containing per litre 6 to 10 g. of sodium sulphate, 0.5 to 1 g. of an oleylpolyglycol ether prepared with 50 mol of ethyleneoxide, to 15 g. of dimethylbenzyl-dodecylammoniurnchloride and 0.3 g. of the dyestutf of Example l'cyanoethyl'z'phenylmdole Reddlsh Violet 10 and which has been adjusted to a pH of 4 to 5 with Instead of 4-aminobenzophenone the nuclearly substiacetic acid. The liquor-to-goods ratio is 40:1. The tempertuted 4-aminobenzophenones can be reacted with the inature of the dye-bath is heated within 30 minutes to 120 doles in the described manner thus yielding the following C. and the bath kept at this temperature for 60 minutes. shades: The dyed fibres are subsequently rinsed with water and Shade on poly- Benzophenones Indolos acrylonitrile 4-amino-3,5-dibromo-benzophenone 1,2-dimethylindole Bluish pink. 4-amino-3'bromobenzophenone do Reddish bordeanx. 4-amino-3,fi-dibromo-benzophenone l-methyl-Z-phenylindo Reddish violet.

Do- Z-metltylindole Bluish pink. 4-an1ino-2-ehlorobenzophenono 1,24iimethylindole Bluish red. d-arnino-i'-methoxybenzophenone do Re 0. 2.1nethylindo1e Red. Do Lmethyl-Z-phenylindo Red-bordeaux. 4-amino-2,5'-d methylbenzophenone do Reddish violet.

Do. 2-rnethylindole Bluish ruby. Do 1,2-dimethylindole Do.

EXAMPLE 14 dried. One obtains a bluish green dyeing of very good fast- A stock solution is prepared from 15 parts by weight Hess propemes of the dyestuff mentioned in Example 11, 15 parts by 9 daestuffs g i l f qg qg may weight polyacrylonitrile and 70 parts by weight dimethyll fwlse ga or t g. yemg 8 5 ig z l formamide, this solution is added to a conventional spin- 40 yester res accor mg 6 met Dds hescn ning solution of acrylonitrile and spun in known manner. 9 16 a 17 thus yleldmg valuable s ades w t A bluish green dyeing of very good fasmess Properties is are similar or equal to the shades obtained on polyacrylics. obtained. We

EXAMPLE 1. AH ammodiphenyl-indolyl-methane dyestutf free of sulfomc acid and carboxylic acid groups having the for- Fibres of polyacrylonitrile are introduced at 40 C. l into an aqueous bath having a goods-to-liquor ratio 1:40 (K) R and containing, per litre, 0.75 g. 30% acetic acid, 0.38 g. D sodium acetate and 0.3 g. of an aminodiphenyl-indolyl- R methane dyestutf, the preparation of which is described below. The bath is heated to boiling temperature within 5 20-30 minutes and kept at the same temperature for (L). 60 minutes. The polyacrylonitrile fibres are subsequently C X- rinsed and dried. They are dyed in a Bordeaux shade of very good fastness properties.

The dyestuff was obtained in the following manner: 10 parts by weight 4-dimethylamino-4'-methoxybenzophenone and 5.7 parts by weight 1,2-dimethylindo1e are l stirred with 15 parts by weight phosphorus oxychloride at 100 C. for 2 hours. The hot melt is stirred into 500 wherein parts by volume of water. The dyestuff is then salted out R is hydrogen; lower alkyl containing 1-5 carbon with 20 parts by weight of sodium chloride. The aqueous atoms; nitro; cyano; benzyl; phenyl; carboxylic acid solution is separated from the dye resin, the dyestuif dismethyl ester; carboxylic acid ethyl ester; unsubstisolved in 500 parts of boiling Water and precipitated with tuted carbonamido; substituted carbonamido con- 10 parts by weight of zinc chloride and 20 parts by weight tainin N-sllbstituents S eted om the group Conof sodium chloride in the form of a zinc double salt. sisting of lower y and lower alkyl Subst tuted EXAMPLE 16 with Cl, Br, or OH; methylsulfonyl; ethylsulfonyl;

phenylsulfonyl; p-toluene sufonyl; benzoyl; or ace- Acid-modified polyglycol terephthalate fibres of the type tyl; Dacron 64 (E. I. du Pont de Nemours and Company) R and R are both hydrogen; or R is unsubstituted and as, for instance, described in the Belgian patent spelower alkyl containing 1-5 carbon atoms; substituted cification 549,179 and the US. patent specification 2,893; lower alkyl containing 1-5 carbon atoms and substi- 816 are introduced at 20 C. into a dye-bath containing tuted with Cl, Br or OH; benzyl, naphthyl; phenyl or per litre 3 g. of sodium sulphate, 0.5 to 2 g. of an oleyl-- phenyl substituted with Cl, Br, lower alkyl or lower polyglycol ether, prepared with 50 mol of ethyleneoxide, alkoxy; and R is unsubstituted lower alkyl contain- 2.5 to 5 g. of diphenyl and 0.3 g. of the dyestutf of Exing 1-5 carbon atoms; substituted lower alkyl contain- 29 ing 1-5 carbon atoms and substituted with Cl, -Br, OH, or CN; or benzyl;

R is hydrogen, lower alkyl containing 1-5 carbon atoms; lower alkoxy; phenyl; phenyl substituted with chlorine, bromine, lower alkyl or lower alkoxy; or carboxylic acid methyl or ethyl ester;

R is hydrogen, lower alkyl containing 1-5 carbon atoms; lower alkyl containing 1-5 carbon atoms substituted with CN; or benzyl;

K, L and M are independently selected from the group consisting of hydrogen; lower alkyl; lower alkoxy; nitro; Cl; and Br; or two of the substituents M are fused to form a naphthalene nucleus;

p, q and r are 1 or 2; and

X is a substantially colorless anion which does not impair the solubility of the dyestufr in an undesirable manner.

2. A dyestufi of claim 1 having the formula wherein R is hydrogen or lower alkyl;

R' is hydrogen, lower alkyl, benzyl, phenyl or phenyl substituted with one or two members selected from the class consisting of chlorine, bromine, lower alkyl and lower alkoxy;

R' is hydrogen, lower alkyl or benzyl;

R' is methyl, phenyl or phenyl substituted by one member selected from the class consisting of chlorine, bromine, lower alkyl and lower alkoxy;

R, is hydrogen, lower alkyl or benzyl; and

Z is chlorine, bromine, lower alkyl or lower alkoxy;

X- is an organic anion.

3. A dyestuff of claim 1 having the formula wherein Z is hydrogen or chlorine;

R" is methyl or phenyl;

'R" is hydrogen, lower alkyl, phenyl or lower alkoxy substituted phenyl;

R"; is hydrogen or lower alkyl; and

n is the number 0, 1, 2 or 3;

X- is an organic anion.

4. The dyestuffiof claim 1 having the formula 5. The dyestuff of claim 1 having the formula 6. The dyestufi' of claim 1 having the formula 7. The dyestuif of claim 1 having the formula C-CH;

8. The dyestufl of claim 1 having the formula 9. The dyestuff of claim 1 having the formula QYONHZ 31 10. The dyestuif of claim 1 having the formula 11. The dyestufl of claim 1 having the formula \-C1 @NKIHQ T C Cl- Q CH3 12. The dyestufi of claim 1 having the formula 13. The dyestuff of claim 1 having the formula References Cited UNITED STATES PATENTS 4/1961 Kranz 260-308 FOREIGN PATENTS 7/ 1914 Germany. 3 1915 Germany. 5/ 19 33 Germany.

ALEX MAZEL, Primary Examiner J. A. NARCAVAGE, Assistant Examiner U.S. C1. XJR.

8-4, 12; 10622; 260- R; 41 C; 88.7 B; 326.12 R; 326.13 R; 326.14 R

Patent No. 3 I g Dated February 15, 1972 Inventor-(s) RAUE' ET It is certified that error appears in the above-identified patent and that said Letters Patent'are hereby corrected as shown below:

The title should read --AMINODIPHENYLINDOLYL-METHANE DYESTUFFS-.

Column 15.33 A v I m 1 Formula I C R" should read @C C R R I R4 1 58- "penyl" should be --phenyl--.

2 Formula III I should read 1:1

6 FormulaIX 4 "R" should read --R3'''''@.

7 Formula X "R" should read --R l0 Table B Y "4-N-phenyl-methylaminophenyl-" should i read 4-N-phenyl-N-methylaminophenyl- 8 i a I"Hade on" should read--Shade on--.

n 2- h 1-5-methylind" should read ---l-ethyl-2--phenyl-5methylindole-.

v 29 I 1 48 aud "X' is an organic anion" should read ---X' is an inorganic or organic anion--.

I A 31 Formula ,"1}1-" should read -C I- Signed and sealed this 22nd day of January 197L (SEAL) Attest:

EDWARD M. FLETCHER, JR. RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents FORM P I USCOMM-DC 60376-P69 

